S,s-bis-benzyl alkylphosphonates

ABSTRACT

S,S-bis-benzyl-alkylphosphonates and S,S-bis-benzylalkylthiophosphonates, each of them optionally unsubstituted or substituted in the aromatic nucleus of the benzyl group, are effective fungicidal agents, preferably for combatting plantpathogenic fungi. They may be used in fungicidal preparations.

United States Patent 1 Beriger [451 Feb. 18,1975

[ S,S-BIS-BENZYL ALKYLPHOSPHONATES [75] Inventor: Ernst Beriger,Neu-Allschwil, Switzerland [30] Foreign Application Priority Data Apr. 2, 1969 Switzerland 5107/69 [52] US. Cl. 260/961, 260/543 P, 260/940, 260/954, 260/955, 424/210, 424/218, 424/22 I [51] Int. Cl C07f 9/40, AOln 9/36 [58] Field of Search 260/961 [56] References Cited UNITED STATES PATENTS 3,094,405 6/1963 Toy et a1 260/961 X 3,185,721 5/1965 Schrader 260/961 X FOREIGN PATENTS OR APPLICATIONS 27,353 11/1968 Japan 260/961 Primary ExaminerAnton H. Sutto 4 Attorney, Agent, or FirmFrederick H. Rabin; Philip P. Berestecki; Harry Goldsmith [57] ABSTRACT S,S-bis-benzyl-alkylphosphonates and S,S-bis-benzylalk ylthiophosphonates, each of them optionally unsubstituted or substituted in the aromatic nucleus of the benzyl group, are effective fungicidal agents, preferably for combatting plant-pathogenic fungi. They may be used in fungicidal preparations.

2 Claims, N0 Drawings 1 S,S-BlS-BENZYL ALKYLPHOSPHONATES This invention relates to phosphonic acid esters, a process for their preparation and fungicidal preparations containing them.

The present invention provides compounds of the general formula in which X represents an oxygen atom or a sulphur atom, R represents an unsubstituted or substituted lower alkyl or aralkyl group, R and R which may be the same or different, each represents a hydrogen atom, a lower'alkyl group, a nitro group, a trifiuoromethyl group, a cyano group, or a halogen atom and m and n, which may be the same or different, each is l or 2.

R preferably represents a lower alkyl group and X preferably represents an oxygen atom.

The present invention also provides a process for the preparation of the compounds of the general formula I, which comprises reacting 1 mole of an alkane-(thio)- phosphonic acid dihalide of the formula HS-CI-HQ or Its-on,

in which R R n and m have the meanings specified above, or if the final product is to be a phosphonic acid ester with dissimilarly substituted benzyl residues, with 1 mole of one of the above-specified benzylmercaptans and then with 1 mole of the other above-specified benzylmercaptans, in the presence of an acid acceptor.

Suitable acid acceptors are, for example, triethylamine, alkali metal carbonates, hydroxides and alcoholates. The exothermic reaction is preferably carried out while slightly cooling the mixture.

The compounds of the present invention have a very good activity against the class Phycomycetes, for example, phytopathogenic fungi, for example Botrytis and Piricularia, and also against various other phytopathogenic fungi that attack grain crops, corn, rice, vegetables, horticultural and othercultures.

The compounds of the present invention are especially active against the following types of fungi:

Cochliobolus miyabeanus species, Corticium species, Cerospora species, Alternaria species, Venturia inaequalis, Podosphaera Leucotricha, Uromyces phaseoli, Cercospora apii, Cercospora beticula, Cercospora musae,

Piricularia sp., Erysiphe cichoracearum, Penicillium digitalum, Sphaerotheca humuli, Diplocarpon rosae, Uncinula necator, Coccomyces hiemalis, Cladosporium carpophilum, Erysiphe graminis hordei, Monolinia (Sclerolinia) Laxa, Monolinia (Sclerotinia) fructicola, Piricularia oryzae, Puccinia recondita, P. coronata, P. glumarum, Puccirzia gramiriis tritici, Aspergillus niger, Aspergillus terreus, Rhizoclonia, Fusarium, Verticillium, but

ity against fungi that attack plants in the soil and some of which cause Tracheomycoses, such as Fusarium cubertse, F usarium dianthi, Verlicillium alboiztrum and Phialophora cinerecens.

The present invention also provides fungicidal preparations which comprise, as active ingredient. at least one compound of the general formula I, if desired, together with a solvent, diluent, dispersant, emulsifier. adhesive, thickenenfertilizer or pesticide, or a mixture of any two or more of said substances.-

Preparations that contain the active substances of the formula I may be applied in the most diverse forms, for example in the form of aqueous sprays, dusting powders or the like.

Aqueous sprays can be prepared, for example, on the basis of an emulsifiable concentrate or wettable powder. A-suitable emulsifiable concentrate can be manufactured, for example, from about 25 parts of a coma mixture of such solvents, and from 2 to 10 parts of one or more emulsifiers. It is also possible to incorporate a small quantity of an agent that promotes the for- 1 mation of a homogeneous solution, for example, methanol, methoxymethanol or butoxymethanol.

A suitable emulsifier may consist, for example, of from 1 to 1.5 parts of calcium or sodium dodecylbenzenesulphonate, from 2.5 to 4 parts of an octylor nonyl-phenoxy-polyethoxyethanol and from about 0.5 to 1 part of methanol and up to 0.8 part of xylene. The resulting mixture is added to the solvents and the active substance of the formula I in the ratio indicated above. It is also possible to use one or more other surfactants. Any type of surfactant as maybe desired or advantageous may be used, for example, an anionic or cationic or nonionic product, which is soluble in solvents, to act as emulsifier. Instead of the above-mentioned nonionic product derived from an alkylphenol and ethylene oxide there may be used, for example, ethylene oxide condensates of long-chain alcohols, carboxylic acids, phenols or amines. Compounds of this type are commercially available. Non-ionic condensates of polyglycerins and a resin-forming acid, for example, phthalic acid, may also be used in the manufacture of self-emulsifying preparations. Typical anionic emulsifiers are those based on alcohol sulphonates, sulphates or sulphosuccinates. Cationic surfactants soluble in solvents are, for example, oleyl benzyl dimethyl ammonium chloride and dodecyl benzyl trimethylammonium chloride or bromide. The character of the emulsifier in the individual case is not especially important, so long as it is soluble in a solution of the active substance in one or more inert organic solvents.

A wettable powder can be prepared by taking up an active substance of the general formula I in a volatile solvent, for example, acetone, and mixing in a finely divided solid, for example, kaolin, pyrophyllite or diatomaceous earth while evaporating the solvent. The powder is heated with a small proportion of one or more wetting-dispersing agents. A suitable formulation con- 5 sists, for example, of 20 parts of an active substance of the formula I, 77.5 parts of one or more finely divided solids, 0.5 part of'wetting agent, for example, an octylphenoxy-polyethoxyethanol, and 2 parts of the sodium salt of methylene-bis-naphthalene-disulphonic acid.

Dusting agents containing from 5 to 10 percent of the active ingredient can be prepared by diluting such a wettable powder with a finely divided solid carrier. If desired, the wetting agent may be omitted. If desired, the dispersant can also be omitted or replaced by a difl5 ferent one.

Each of the fungicidal preparations described above contains, in general, a carrier and, in most cases, a surfactant. Y

The fungicidal preparations of the present invention may be used by themselves or in admixture with other fungicidally active substances, among which may be mentioned, for example, the following:

Copper compounds, for example,

copper-l-oxide (cuprous oxide),

Bordeaux mixture,

copper-ll-sulphate pentahydrate (copper sulphate),

basic copper-ll-chloride (copper oxychloride),

copper-Il-phosphate,

tribasic copper-ll-sulphate,

basic copper-ll-carbonate,

copper-lI-dihydrazine sulphate,

copper-amine complexes,

copper-II-sulphate+ammonium carbonate mixture,

copper-ll-chloride+basic copper-[I-sulphate mixture,

basic copper-ll-carbonate-kzinc salt mixture,

copper-Il-zinc chromatic complex (copper zinc chromate),

copper-lI-zinc cadmium-calcium chromate complex,

copper-Il-salt of oleic acid (copper oleate),

copp'er-lI-salts of fatty acids, copper-II-salt of naphthenic acid (copper naphthenate),

copper-Il-salt of 8-hydroxyquinoline (oxine copper),

copper-ll-salt of l,Z-naphthoquinoxime-(Z),

copper-Il-salt of 3-phenylsalicylate;

tin and mercury compounds, for example,

bis (tri-n-butyl-tin)oxide,

triphenyl-tin hydroxide (fentin hydroxide),

triphenyl-tin acetate (fentin acetate),

bis-(tributyl-tin)succinate,

mercury-I-chloride (calomel),

mercury-lI-chloride (mercuric chloride),

mercury-lI-oxide,

mercury-zinc chromate complex,

mercury-lI-lactate,

ethylmercuric chloride,

2-hydroxyethyl-mercuric acetate,

ethylmercuric isothiocyanate, 60

3-ethoxypropyl mercuric bromide,

chloromethoxypropyl mercuric acetate, methoxyethylmercuric chloride, 2-methoxyethylmercuric silicate,

bis-(methylmercuric)sulphate, 65

bis-(methylmercuric)ammonium acetate,

ethylmercuric acetate,

2-methoxyethylmercuric acetate,

ethylmercuric phosphate.

isopropylmethylmercuric acetate,

methylmercuric cyanide,

methylmercuric benzoate,

N-cyano-N-(methylmercuric)guanidine,

methylmercuric pentachlorophenolate,

ethy|mercuric-2,3-dihydroxypropylmercaptide,

methylmercuric-8-hydroxyquinolate (Ortho LM),

N-(methylmercuric)-l ,4,5,6,7,7-hexachlorobicyclo- [2.2.1]-hept-5-ene-2,3,-dicarboximide,

N-(ethylmercuric)-l ,4,5,6,7,7-hexachlorobicyclo- [2.2.1]-hept-5-ene-2,3-dicarboximide,

sodium salt of ethylmercuric thiosalicylate,

N (ethylmercuric)-para-toluenesulphonic acid anilide,

phenylmercuric acetate (PAM),

phenylmercuric propionate,

phenylmercuric triethanol ammonium lactate (PAS),

phenylmercuric urea,

N-(phenylmercuric)- l ,4,5 ,6,7,7-hexachlorobicyclo- [2.2.1l-hept-S-ene-Z,3-dicarboximide,

phenylmercuric dimethyl dithiocarbamate,

phenylmercuric formamide,

phenylmercuric chloride,

phenylmercuric acetate, benzoate, borate, hydroxide, iodide,

basic phenylmercuric nitrate,

phenylmercuric monoethanolamine lactate,

phenylmercuric salicylate,

hydroxymercuric chlorophenol, trichlorophenol, ni-

trophenol,

N-phenylmercuric ethylenediamine,

' phenylmercuric monoethanolammonium acetate,

pyridylmercuric acetate,

diphenylmercuric-8-hydroxyquinolate,

mercuric-(lI)-complex with organic phosphates,

mixture of methylmercuric-2,3-dihydroxypropylmercaptideand methylmercuric acetate,

mixture .of ethylmercuric-2,3-dihydroxypropylmereaptide and ethylmercuric acetate,

mixture of hydroxymercuric chlorophenol and hydroxymercuric nitrophenol,

mercury-cadmium organic complex;

further inorganic compounds, for example,

elemental sulphur,

ammonium polysulphide,

sodium polysulphide,

barium polysulphide,

calcium polysulphide and calcium thiosulphate (lime sulphur),

calcium hypochlorite,

boric acid,

sodium tetraborate decahydrate (borax),

zinc chloride,

magnesium borate,

nickel sulphate,

potassium chromate,

lead arsenate,

cadmium chloride,

cadmium carbonate,

further organo-metal compounds, for example,

cadmium succinate,

cadmium-din-propyl-xanthate,

cadmium-8-hydroxyquinolate,

phenylamino-cadmium acetate,

phenylamino-cadmium dilactate',

methyl arsine sulphide,

zinc, octate, oleate;

simple aliphatic organic compounds, for example,

formaldehyde, paraformaldehyde,

acrolein,

methylbromide,

methyl isothiocyanate,

tetraiodoethylene,

l,3-dichlropropene and related chlorinated hydrocarbons,

l-chloro-3-bromopene( l transl ,4-dibr0mobutene(2),

1,3-dichloropropene( l l-chloro-2-nitropropane 2-chloro-l -nitropropane trichloronitromethane,

dichloro tetrafluoro acetone,

sodium salt of propionic acid,

calcium salt of propionic acid,

chlorofumaric acid-bis-B-chloroethyl ester,

sorbic acid and its potassium salt,

2-propene1,l-diolacetate,

2-aminobutane,

dodecylguanidineacetate (dodine), -phthalate,

a-chloroacetyl-l ,3-aminopropionitrile,

a-bromoacetylvalinamide,

1,2-dichloro-l-(methylsulphonyl)-ethylene,

-(methylsulph0nl)-ethylene,

l,2-dichlorol -(butylsulphonyl)-ethylene,

transl ,2-bis-( n-propylsulphonyl )-ethylene,

benzene derivatives, for example,

para-dichlorobenzene,

hectachlorobenzene (HCB),

1,2,4,5-tetrachloro-4-nitrobenzene (tecnazene),

pentachloro-nitrobenzene (quintozene),

1,3 ,5 -trichloro-2,4,6-trinitrobenzene,

isomer mixture of l,3,4-trichloro-2,-dinitrobenzene and l,2,3-trichloro-4,6-dinitroberizene,

2,4,5,6-tetrachloroisophthalic acid nitrile,

2,4-dinitrophenyl thiocyanate,

diphenyl (biphenyl),

ortho-nitrodiphenyl,

l-chloro-2 ,4-dinitr0naph thalene,

acenaphthene;

phenols, for example,

2,4,6- and 2,4,5-trichlorophenol, v

2,4,5-trichlorophenyl acetate and chloroacetate,

trichlorophenol-zinc salt,

meta-cresyl acetate,

2,3,4,6-tetrachlorophen0l,

pentachlorophenol (PCP),

ortho-dihydroxybenzene,

2,4-dihydroxy-n-hexylbenzene, v

Z-phenylphenol (orthophenylphenol),

3,5-dibromosalicyladehyde,

2-benzyl-4-chlorophenol,

2,2 '-dihydroxy-5 ,5 '-dichloro-diphenylmethane chlorophene),

2,2'-dihydroxy-3,3,5,5,6,6-hexachlorodiphenylmethane,

2,2 '-dihydroxy-5 ,5 '-dichloro-diphenylsulphide,

2,2-dihydroxy-3,3',5,5-tetrachlorodiphenylsulphide and its disodium salt,

4-chloro-ortho-phenylphenol, v

l,4-dichloro-2,5-dimethoxybenzene (chloroneb) salicylanilide,

bismuth salicylate,

trif'luoromethyl salicylanilide halogenated with chlorine or bromine,

brominated salicylanilide,

(3,5-dimethyl-4-chlorophenoxy)-ethanol;

dinitrophenol derivatives, for example,

2-( l-methyl-n-propyl)4,6-dinitrophenyl-2- methylcrotonate (binapacryl),

2-( l-methyl-n-propyl)-4,6-dinitrophenyl carbonate (dinobuton),

2-( l-methyl-n-heptyl)-4,6 dinitrophenylcrotonate '(dinocap),

methyl-2,6-dinitro-4-( l-ethylhexyl)-phenylcarbonate methyl-2,6-dinitro-4-(l-propylpentyl)phenylcarbonate (dinocton p),

4-nonyl-2,6-dinitro-phenylbutyrate,

S-methyl-2-( l-methyl-n-heptyl)-4,6-

dinitrophenylthiocarbonate;

aniline derivatives, for example,

2,6-dichloro-4-nitroaniline (dichloran),

2-cyanoethyl-N-phenylcarbamate,

propynyl-N-phenylcarbamate,

oz-( 2-brom0acetoxy )-acetani lide;

quinone derivatives, for example,

2,3,5,6-tetrachlorobenzoquinone( 1,4) (chloranil),

2,3-dichloro-naphthoquinone( 1,4) (dichlone 2-amin0-3-chloro-naphthoquinone( 1,4),

2-chloro-3-acetamino-naphthoquinone( 1,4),

4-methyl-2,3 ,5 l O-tetrahydro-3,5, l O-trioxo-4H4-H- naphth0-( 2,3-b )-l ,4-thiazine,

2,3,6,7-tetrachloro-4a,Sa-epoxyl ,2,3,4,4a,8a-

hexahydro-l ,4-methanonaphthalene-5,8-dione,

quinoximbenzoyl hydrazone (benquinox);

trichloromethylthio derivatives, for example,

N-(trichloromethylthio)phthalimide (folpet),

N-(trichloromethylthio)cyclohex 4-ene-l,2-

dicarboximide (captan),

N( 1,1 ,2,2-tetrachloroethylthio)-cyclohex-4-ene- 1,2-dicarb0ximide (captafol),

N-methanesulphonyl-N-trichloromethylthio-parachloraniline,

N-dichlorofluoromethylthio-NN-dimethyl-N'- phenylsulphamide (dichlofluanide),

S-( 2-pyridyll -0xide )-S'-trichloromethyl disulphide hydrochloride;

organic phosphates, for example,

0,0,0-trimethylthio phosphate,

0,0-diethylphthalimid0 phosphono thioate,

isopropyl- 5-amino-bis-( dimethylamido )phosphin-yl-3-phenyl- -zinc-ethylenel ,2-bis-dithi0carbamate (zineb 7-chloro-4-dimethylamino-l,4,4a-5,5a,6,l1,120:-

octahydro-3,6, 1 0, l 2,1 2a-pentahydroxy-o-methyl- 1,1 l-dioxo-2-naphthacene carboximide I (chlortetracyclin), (pimaricin), (lancomycin), (phleomycin), (kasugamycin), (phytoactin), di(-)-threo-2,2-dichloro-N-[B-hydroxy-a- (hydroxymethyl )-paranitropheneethyllacetamide (chloramphenicol), blasticidine-S-benzylamino-benzenesulphonate; N-( 3-nitrophenyl )itaconimide, phenoxyacetic acid, sodium-para-dimethylamino-benzenediazosulphonate, acrolein-phenylhydrazone, 2-chloroacetaldehyde(2,4-dinitrophenyl)- hydrazone, 2-chloro-3-(tolysulphonyl)-propionitrile. l-chloro-Z-phenyl-pentane-diol(4,5 )-thione( 3 para-nonyl-phenoxy polyethyleneoxyethanol-iodine complex, (d-nitromethyl)-ortho-chlorobenzyl thioethylamine I hydrochloride, 3-(para-tertiary butyl-phenylsulphonyl)acrylonitrile, octachloro-cyclohexenone, pentachloro-benzyl alcohol, pentachloro-benzyl acetate, pentachloro-benzaldehyde cyanohydrin, Z-nor-camphan methanol, '2,6-bis-](dimethylaminomethyl)-cyclohexanone,

decachloro-octahydro-l ,3,4-metheno-2H-cyclobuta- V [cdl-pentalen-Z-one, 1-( 3-chlorallyl )-3,5,7-triazal -az'onia-adamantan chloride, coal tar and blast furnace tar; and mixtures of nickel sulphate marieb, maneb mercaptobenzthiazole, zineb mercaptobenzthiazole, zineb nickel-ll-chloride, zineb nickel-ll-sulphate, ziram basic copper sulphate, ziram zinc mercaptobenzthiazole, thiram cadmium chloride hydrate, thiram hydroxymercuric chlorophenol, thiram phenylmercuric acetate, polyethylene-bis-thiuram sulphide copper oxychloride, I methylarsine-bis(dimethyl-dithiocarbamate) ziram thiram, folpet phenylmercuric acetate, dodine ferbam sulphur, dithianone copper oxychloride, dichlone ferbam sulphur, dinocap dinitro-octylphenol, captan quintozene tribasic copper sulphate, cadmium propionate phenylmercuric propionate, formaldehyde urea, 1 phenyl ammonium cadmium dilactate phenylmercuric formamide, and basic copper sulphate zinc salts. The following Examples illustrate the invention, the parts and percentages being by weight, unless otherwise stated.

"EXAMPLE 1 42 parts of triethylamine were dropped at 5 to C ter. The residue obtained after evaporation of the solvent consisted of 52.3 parts of the compound of the formula i CH3P -s0115 11... 1,6275

Compound No. 1

In an analogous manner it is possible to manufacture the compound of the formula s ll CH;'P SCH m 1,6588

Compound No. 2

as well as the following compounds:

Com-

pound Physical numcharacber Formula terlstic E 1t, 1.6648 C1OH2P(SCH2) c13o-P(s-oH,

5 I in," 1.6932

C1CH2P S-CHQ) 2 6 1 A at, 1.6311 CH3-P( s GHQ-o1) 7 iii) j n,. =1.6105

iS0CaH1P s GHQ) s no 1.6259

C2H5P\ SCH2N02 9 l 15488 o so C2H5P\ I CFa 0 SCH C2H5P\ 11 c1 1th 1.6423

(H) l CHa-P SOH2 0l CHa-P SCH -c1 CHa-P(S Hz-Q-CN) Continued {1311 Physical numcharaclmr Formula terlsttc l4 cm nD LGOQQ ll mn- I soml!- a 4. O Smp.:85-90 a Z -cm1*(scH,- 2

ll CzHs-P(SCH ll C2H5P (Sam-@411) ll C1-CHz-CH-P(SCH) ll o1-oHzoH2-P(scH,-oi)

21' CH; nn 1.6099

1i CHz-P SCH:

EXAMPLE 2 I parts ofa compound of the general formula I were taken up in a 25% xylene solution of a mixture of equal parts of a condensation product of about 1 mole of para-tertiary octylphenol and about 10 moles of ethylene oxide and calcium para-dodecyl-benzenesulphonate and the mixture made up with xylene to parts by volume. When this solution is diluted with water to the desired concentration, a stable emulsion is obtained which is very suitable for spraying.

EXAMPLE 3 Compounds Nos. 1 and 7 specified in Example 1 are After one week the treated plants displayed an infestation of 5%, compared with a 100% infestation of the controls.

Compound No. 7 achieved this result even. in a concentration of 0.03% of activesubstance.

I claim:

1. The compound of the formula 2. The compound of the formula 

1. THE COMPOUND OF THE FORMULA
 2. THE COMPOUND OF THE FORMULA 